Lubricating composition of matter



Patented Oct. 21, 1952 LUBRICATING COMPOSITION OF MATTER Denham Harman, Berkeley, and Roy E. Thorpe,

San Francisco, Calif., assignors to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application October 11, 1949, Serial No. 120,828

19 Claims. (Cl. 25249.9)

This invention relates to a novel class of re action products adapted to improve the properties of liquids and/or solids suitable for use as lubricants, coolants, rust and corrosion inhibiting compositions, coating compositions and the like. More particularly this invention pertains to lubricants, such as natural and synthetic lubri" cants, emulsions, aqueous solutions and organic and/or inorganic materials which can be adapted for lubricating purposes, by addition thereto of a novel multifunctional reaction product capable of imparting extreme pressure, anti-wear, antifouling properties, as well as acting as an inhibitor of oxidationand corrosion.

It is well known that various lubricants, whether doped or undoped, tend to oxidize and to form corrosive bodies and sludge, when used for their intended purpose. Some of the deterioration products of lubricants formed during their use are hard carbonaceous materials which adhere to metal surfaces and cause scratching and scufiing of movable metal parts and sticking of valves and piston rings in engines. In addition, presently known lubricants are generally incapable of maintaining a continuous lubricating film between movable parts in many present day machines, resulting in gradual or rapid wearing away of metal parts. The damage thus caused requires replacement of such parts or even the complete overhauling of engines and machines, resulting in loss of production and time.

In the case of mineral lubricating oils which have been highly refined for specific uses, or of synthetic lubricants developed for specific or special uses, it has been observed that such oils or lubricants are generally highly susceptible to oxidation and deterioration, becoming progressively more corrosive in engines and machines even under ordinary operating conditions.

To improve the lubricating properties of oils and synthetic lubricants it has become the practice to blend with various lubricants one, and in most cases more than one, addition agent, which additives have the effect or property of inhibiting deterioration of lubricants and imparting to them certain beneficial properties. Thus, additives have been specifically designed which have the property of inhibiting corrosion of alloyed bearings such as copper-lead, cadmiumsilver and the like, developed for automotive, diesel and aircraft engines. Acidic oxidation or decomposition components formed in lubricants during use readily attack these bearings but are inhibited or prevented from doing this by the formation of a corrosion protective film formed on the bearing surface with the aid of the additive. Additives have also been developed which possess the property of modifying the carbonaceous materials formed by deterioration of lubricants. Such additives modify this carbonaceous material so that it can be removed easily and the tendency of engine parts to become stuck is inhibited so that ringsticking, piston scuffing, scratching and wearing away of other engine parts and material reduction of engine efficiency are prevented or materially inhibited.

Other additives have been developed for the purpose of acting as detergents in lubricants in order to assist in the removal of soot or sludge, varnish and lacquer formed from deterioration of the oil when subjected to high operating temperatures. Detergents prevent the build-up of these deleterious materials on the metal parts and assist in removing those formed. Antiwear additives have the property of reducing friction between movable metal parts thus reducing frictional contact of metals. Also, additives have been developed to withstand extreme pressures, disperse impurities, solubilize certain additives and the like.

Most, if not all additives, are capable of functioning in substantially only one specific manner. Very few lubricant additives have the ability to improve a lubricant in more than one respect. Thus, a good anti-oxidant might not be able to inhibit lacquer and varnish formation on piston rods or act as a detergent or as corrosion inhibitor. In many cases it is found that an additive possesses very good properties in one respect, but is actually detrimental as an additive in another respect. Therefore, other additives are frequently required to Obtain a satisfactory lubricant. The combination of additives in lubricants wherein each additive exerts its influence without interfering with the function of other additives is a difiicult matter to attain. In most cases additives co-react or interfere with each other. To prevent this, great care must be taken in selecting the additives, mixing them in specific proportions and continuously watching and rep-lacing additives which have stopped functioning or have deteriorated.

Additives which are used in lubricants for industrial purposes, such as in cutting, drawing, quenching, and rolling operations, must impart to said lubricants film strength, corrosion inhibiting and detergent properties as well as aid the base lubricant to cool and lubricate the base metal or other surfaces under the most adverse conditions of lubrication and the like.

It is an object of this invention to improve the lubricating properties of various lubricating bases by the addition thereto of a minor amount of a mixture of multi-functional materials. Another object of this invention is to add to compounded or doped lubricants multi-functional material whereby a synergistic effect is produced, resulting in a product of accentuated and improved properties. Another object of this invention is to add 3 to oleaginous materials, organic and inorganic lubricants, mineral lubricating oils, synthetic lubricants and the like, multi-functional materials so as to inhibit oxidation and corrosion and prevent the formation of sludge, varnish and lacquer in said lubricants even under adverse operating conditions. Still another object of this invention is to use in lubricating compositions multi-functional materials which prevents ringsticking as Well as the sticking of other engine parts due to deterioration of the lubricant. Also, it is an object of this invention to use in oleaginous materials, e. g. in lubricating compositions, multi-functional materials which inhibits wear, scuffing, scratching and other damage to engine parts. Also it is an object of this invention to improve the lubricating and cooling properties of base materials adapted for use in cutting, quenching, drawing and rolling operations by addition to said base materials of a multi-functional materials of this invention. Furthermore, it is an object of this invention to provide novel multifunctional improving and enhancing additives for lubricating bases. Other objects of this invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, it has noW been found that the addition of minor amounts of two particular types of additives to suitable vehicles, the combination of which produces a synergistic efiect, results in a composition having outstanding extreme pressure properties, lubricity and stability. The two additives which so function in accordance with this invention are, first, certain polyhaloorganophosphonates in combination with, second, certain organophosphonic or phosphinic acids or polyhaloorganop-hosphonic or phosphinic acids. The polyhaloorganophosphonates of this invention can be represented by the general formula:

wherein X is an element from the group consisting of O, S, Se and Te; R and R1 may be the same or different and are selected from the group consisting of organic radicals such as alkyl (both acyclic and alicyclic), aryl, alkaryl and aralkyl hydrocarbon radicals and polar-substituted derivative radicals thereof or cationic radicals, inorganic or organic radicals. If the radicals R and R1 do contain polar groups, these polar groups may be the halo atoms (Cl, Br, I, F) or OH, SH, NHz, N02, N--NO, CN, SOsI-I, etc., radicals. The radical R2 is an organic radical such as alkyl (either acyclic or alicyclic) aryl, aralkyl and alkaryl hydrocarbon radical containing polyhalogens, preferably not more than four carbon atoms removed from the phosphorus atom, said radical R3 being linked directly to the phosphorus atom through a carbon atom. Specific illustrative examples of the radicals R and R1 are: methyl, ethyl, butyl, amyl, octyl, stearyl, allyl, oleyl, phenyl, cresyl, naphthyl, cyclopentyl, cyclohexyl, cyclohexylethyl, phenyl, cyclohexyl, cyclohexylphenyl, methyl cyclohexyl, cetyl cyclohexyl, phenylethyl, benzyl, cetyl-phenyl, ethyl naphthyl; methoxy phenyl; ethoxy phenyl, methyl mercapto phenyl, selenomethoxy phenyl, selenoethyloxy phenyl, telluro methoxy phenyl, thiolauroxy phenyl, selenolauroxy phenyl; acetyl-phenyl,

lanoyl phenyl, stearoyl phenyl, stearoyl ethyl, lauroxyl ethyl; chloro octyl, dichloro phenyl, bromoethyl-phenyl, amino-octyl, amino-acetylphenyl, cyanoethyl naphthyl, nitrocetyl-phenyl,

nitro-oleyl, etc. The radical R2 is specifically illustrated by the polychloro, polybromo and polyfiuoro alkanyl and alkenyl (acyclic and alicyclic) containing from 1 to 20 carbon atoms, e. g., diand tri-chloroor bromomethyl, propyl, amyl, octyl, cetyl, hexadecyl, and nonadecyl, as well as dichloro ethenyl, trichloropropenyl, etc. It is preferred that at least one and preferably all of the halo atoms be not more than four carbon atoms removed from the phosphorus atom. In addition, R2 can be illustrated by such radicals as dichlorophenyl, dichloroethylphenyl, trichloromethylphenyl, cyclohexyl dichlorobutyl, cyclohexyl dibromobutyl, etc.

The halophosphonates as represented by the above formula can be prepared by reacting suitable phosphite esters such as are disclosed in the following U. S. Patents: 2,084,270, 2,230,543, 2,241,243, 2,365,291, 2,432,093, with a polyhalogenated organic compound such as: carbon tetrachloride, chloroform, methylene chloride, carbon tetrabromide, bromoform, methylene bromide, iodoform, methylene chloroiodide, hexachloroethane, trichloroethane. Polyhalogenated fatty acids in which the halo radicals are preferably attached in the alpha or beta position to the carboxyl radical may be used, such as: dichloroacetic acid, trichloroacetic acid, alpha,alphadichloropropionic acid, alpha,alpha,beta,betatetrachloropropionic acid, alpha,beta-dichloropropionic acid, alpha,alpha-dichlorobutyric acid, alpha,beta dichlorobutyric acid, alpha,alpha,- beta-trichlorobutyric acid, alpha,beta-dichloroisobutyric acid, phenyl dichloroacetic acid, dibromoacetic acid, tribromoacetic acid, alpha,- alpha dichloropentanoic acid, alpl1a,alpha-dibromopentanoic acid, diiodacetic acid, triiodacetic acid, beta,beta-dibromopropionic acid, alpha,- alpha-dichlorocaprylic acid. Other polyhalogenated oxy-organic compounds may be used, such as polyhalogenated aldehydes, ketones, and ethers, e. g., chloral, bromal, trichlorobutanone, polychloromethyl isobutyl ketone dichloroethyl ether and the like.

The following examples are illustrative of the preparation of the polyhalophosphonate esters of the invention:

EXAMPLE I A desired reaction product of this invention Was prepared by refluxing about 50 gm. of triethyl phosphite with about 250 cc. of dry carbon tetrachloride. A colorless solution was formed which was distilled under reduced pressure to yield a colorless mobile liquid, diethyl trichloromethanephosphonate, having a boiling point of about 121 C. at 11 mm. of Hg pressure and an index of refraction (11. of 1.4628. The reaction may be represented by the equation:

About 50 gm. of tributyl phosphite were heated with about 130 gm. of l- -bromo-3-chloropropane at a temperature of between 113 C. and 118 C. for a period of about 16hours to produce as a reaction product, dibutyl 3-chloropropane-lphosphonate. This product had a boiling temperature of about 200 C. at 2 mm. of mercury pressure, and a refractive index (n of 1.4472. The reaction may be represented as follows:

About 46 gm. of ethyl trichloroacetate and about 40 gm. of triethyl phosphate were heated for about five hours at a temperature of about 100 C. The somewhat dark-colored reaction product thus produced was then distilled under a vacuum to give a water-White distillate frac-- tion having a boiling temperature of from 108 C. to 109.5" C. at 2 mm. of mercury pressure, and a refractive index (n of 1.4505. This-reaction product is represented by the formula:

A mixture of sym-dichlorodiethyl ether and tributyl phosphite were reacted for about 16 hours at about 155 C. under substantially the same conditions as described in the previous examples. The resultant reaction yielded dibutyl (2-chloroethoxy)-2-ethane-1-phosphonate having a boiling point between about 145 and 147 C. at 0.5 mm. pressure and a n of 1.4472. The chemical formula of this product is Other examples of halophosphonates which can be used to improve the lubricating properties of various materials or as additives in hydraulic fluids, greases, fuels, heat-transfer medias, etc...

are:

Chlorobutylphenyl dichloropropanephosphonate Diethyl trichlorocyclohexane phosphonate Dibutyl dichlorocyclohexane phosphonate Di(ch1orocresyl) trichloromethanephosphonate Diethyl trichloromethanethiophosphonate Dibutyl trichromethanethiophosphonate Dicyclohexyl trichloroethanethiophosphonate Diallyl dichlorobutanethiophosphonate Dibutyl trichloromethaneselenophosphonate Salts of the above halophosphonatescan be formed by treating said compounds with organic bases, e. g. amines or metal oxides, hydroxides, carbonates, and the-like. Preferred are the Na, Li, K, Ca, Ba, Sr, Mg, Zn, -Al, Sn, Co and Ni salts of said halophosphonates or the diethylamine, triethanolamine, octylamine, stearylamine salts of said haloph-osphonates.

The second additives used in compositions of this invention are organophosphonic, organophosphinic, haloorganophosphonic and/or polyhaloorganophosphinic acids. The haloorganophosphonic acids can be produced from the abovementioned esters by hydrolysis and/or pyrolysis or by treating the esters in presence of HCl or HBr at an elevated temperature, ranging from to 200 C. and preferably from about to C. The polyhaloorganophosphonic acids may be represented by the formula:

Ra-i

wherein R3 and X are the same as R2 and X or R3 can be an alkyl, aryl, aralkyl, alkaryl or cyclic radical without any substituent halogen atoms as defined in the previous formula for the haloorganophosphonates.

Illustrative examples of suitable haloorganophosphonic acids are: I

Trichloromethanephosphonic acid Dichloroethanephosphonic acid Trichloroethanephosphonic acid Tribromomethanephosphonic acid Dichloromonobromomethanephosphonic acid Dibromobutanephosphom'c acid Dichlorophenylethanephosphonic acid Trichlorocyclohexane phosphonic acid Dichlorocyclohexane phosphonic acid Dichloropropane phosphonic acid Tribromopropane phosphonic acid Dichloroethene phosphonic acid Dichloro phenyl benzene phosphonic acid Dichloromonobromobutanephosphonic acid Dichlorooctanephosphonic acid Trichloromethanethiophosphonic acid Dibromobutanethiophosphonic acid Trichlorocyclohexanethiophosphonic acid Dichloroethenethiophosphonic acid Trichloromethaneselenophosphonic acid Benzenephosphonic acid, octadecanephosphonic acid If desired, the organo phosphinic acids or the haloorgano phosphinic acids may be used and such acids may be represented by the general formula:

T RaP-XH 1%. wherein R3 and X are the same as defined above while R4 can be hydrogen Or the same as R, R1. R2 or R3 as already defined.

The phosphinic acids are prepared by addition of sodium hypophosphite to unsaturated organic compounds followed by acidification as illustrated in the following example:

EXAMPLE VI About 0.4 mole of sodium hypophosphite and about 0.4 mole of l-octene were added to 100 moles of methanol containing 0.0018 mole of 2,2- bis(tert-butyl peroxy) butane and the mixture reactedin an enclosed pressure-resistant vessel at a temperature of about 120 C. for about two hours under agitation. At the end of the reaction a single phase colorless liquid was observed which was sodium octane-l-phosphonate. This salt was acidified to form the octane phosphinic acid.

To form the halo alkane phosphinic acids, the corresponding halo alkenes should be used.

Illustrative examples of polyhalo organic phosphinic acids are:

Trichloromethanephosphinic acid Trichloromethanethiophosphinic acid Dibromoethanephosphinic acid Trichlorocyclchexanephosphinic acid Dichlorohexadecanephosphinic acid Hexadecanephosphinic acid The esters and acids of this invention may be used in amounts ranging from 0.01% to 10% and preferably from 0.1% to about by Weight, respectively. The ratio of the ester to the acid may vary from 0.5 (1:2) to (10:1) and preferably from 1:2 to 2:1, respectively.

The vehicles to which reaction products of this invention may be added for purposes of improving the lubricating qualities of said vehicles or for purposes of producing corrosion-protective compositions and the like may be divided into several groups.

The vehicles should preferably be substantially neutral, although they may be Weakly acidic or basic, preferably having acidic or basic dissociation constants not above 10-. Both polar and non-polar vehicles may be employed. Among the former are water; water-soluble and water-insoluble alcohols such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, oyclohexyl, methylcyclohexyl, lauryl, cetyl, stearyl, oleyl, allyl, benzyl, etc., alcohols; monomeric polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, cetene glycol, glycerol, methyl glycerol, etc.; phenols and various alkyl phenols and thiophenols; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl butyl ketone, dipropyl ketone, cyclohexanone, and higher ketones; keto alcohols; ethers such as diethyl ether, diisopropyl ether, betabeta-dichlorodiethyl ether, diphenyl oxide, chlorinated diphenyl oxide, diethylene glycol, triethylene glycol; neutralesters of carboxylic and other acids such as ethyl, propyl, butyl, amyl, octyl, stearyLoleyl, phenyl, cresyl and higher acetates, propionates, butyrates, lactates, laurates, mYristateS, palmitates, stearates, oleates, ricinoleates, phthalates, salicylates, carbonates; natural Waxes such as carnauba wax, candelilla wax, Japan Wax, jojoba oil, sperm oil; fats such as tallow, lard oil, olive oil, cottonseed oil, Perilla oil, linseed oil, tung oil, soya bean oil, flaxseed oil, castor oil, etc.; as Well as fractions and derivatives thereof.

Vehicles of little or no polarity comprise hydrocarbons such as liquid butanes, pentanes, hexanes, heptanes, octanes, octenes, benzene, toluene, xylene, cumene, indene, hydrindene, alkyl naphthalenes, gasoline, kerosene, hydrocarbon fuel oil, gas oil, turbine oil, motor oil, mineral spirits, aromatic solvents, petroleum lubricating oils which may or may not be defined as by solvent extraction, and treatment, etc., and which may be soap thickened to form greases, petrolatum, paraffin waxes, albino asphalts, etc.

Also, synthetic oils may be used as the vehicles, such as polymerized olefins, polymers and copolymers of alkylene glycols and alkylene oxides; organic esters, e. g. Z-ethyl hexyl sebacate, allyl laurate, and polymers thereof; dioctyl phthalate, trioctyl phosphate, polymeric tetrahydroluran, polyalkyl siloxanes and silicates, and the like. Mixtures of synthetic and natural lubricants and oils may be used. In addition, resinous materials such as petroleum resins, natural resins as rosin, resins formed by polymerization of drying fatty oils, phenol-formaldehyde resins, glyptal-type resins formed by esterification of polyhydric alcohols with polycarboxylic acids can be used.

Still another class of vehicles to which condensation products of this invention are suitably added are water-in-oil and oil-in-water emulsions suitable for various uses such as lubricating, cooling, rust inhibiting, and the like, as well as hydraulic fluids, heat transfer fluids, fireproofing compositions, agricultural acids such as insecticides, fungicides, etc.

The following table illustrates specific compositions of this invention, each component of which may be used in amounts indicated above and hereinafter.

Composition Components Primary Additive- Ester:

d iethyl trichloromethanephostrichloromethanephosphonate dicyclohexyl trichloropropanephosphonate dicresyl dichloropropanephosphonate dlallyl pentachlorocyclohexanephosphonatc 1 The secondary additives as listed above and those presented hereinafter can be used in amounts varying from 0.01% to 2% and higher. The primary additives are used in amounts indicated and the base constitutes the balance of the composition.

2 Containing 15% of polymeric ester of acrylic acid and 1% phenyl-alpha-naphthyl amine.

Compositions of this invention were evaluated as extreme pressure agents by use of the four-ball extreme pressure lubricating tester similar in principle to the Boerlage apparatus described in the magazine, Engineering, volume 136, July 13, 1933. This apparatus comprises four steel balls arranged in a pyramid formation. The top ball is rotated by spindles against the three bottom balls which are clamped in a stationary ball holder. The balls are immersed in the composition to be tested. Tests were run under conditions indicated in the following table and compared with other outstanding extreme pressure compounds.

Four-ball evaluation of E. P. compositions of this invention [Fixed Conditions: One minute, 1500 R. P. M. at temperatures as indicated, steel on steeL] S Additive Amoun. car Dlemeter (mm.) at Various Loads (kg.) Semue Base Lubricant Combmation of riddi- Load W 40 50 so so 90 100 110 120 140 160 200 240 260 280 300 (kg) Percent di-Z-ethyl hexyl seba- Composition 19.. 1 .52 .53 .58 .63 .70 70 .81 1.03 240-260 cate containing 15% polymeric ester of accylic acid and 1% of an aryl amine di-2-ethyl hexyl seba- Composition 5.. 1 .60 .91 L 140-150 cate containing 15% polymeric ester of acrylic acid and 1% of an aryl amine 1 Do Di-sec-butyltri- 1 .41 .44 1.69 1.90 80-90 chloromethene phosphonate. Do 40-50 Mineral Oil Composition 1- .73 110-120 Composition 2 .58 81 1.03 240-260 .3 1.80 42-48 P treated .42 .55 .65 .85 55-50 Castor Oil.

1 Phenyl-alpha-naphthy]amine.

L indicates large scars, definitely in seizure range.

To compositions of this invention containing the two primary additives of this invention can be added other additives such as blooming agents, pour point depressors and/or viscosity improvers, antifoaming agents and the like. Among the specific additives for lubricating purposes which are suitably used are oil-soluble detergents which include oil-soluble salts of various bases with detergent-forming acids. Such bases include metal as Well as organic bases. Metallic bases include those of alkali metals, Ca, Mg, Cu, Sr, Ba, Zn, Cd, Al, Sn, Pb, Cr, Mn, Fe, Ni, Co, etc. Organic bases includevarious nitrogen bases as primary, secondary, tertiary and quaternary amines.

Examples of detergent-forming acids are the various fatty acids of, say, 10 to carbon atoms, wool fat acids, paraflin wax acids (produced by oxidation of paraffin wax), chlorinated fatty acids, aromatic hydroxy fatty acids, paraffin wax benzoic acids, various alkyl salicylic acids, phthalic acid monoesters, aromatic keto acids, aromatic ether acids, diphenols as di-(alkylphenol) sulfides and disulfides, methylene bis-alkyl phenols; sulfonic acids such as may be produced by treatment of alkyl aryl hydrocarbons or high boiling petroleum oils with sulfuric acid; sulfuric acid monoesters; arsonic and antimony acid mono and diesters, and the like.

Additional detergents are the alkaline earth phosphate diesters, including the thiophosphate diester; the alkaline earth diphenolates, specifically the calcium and barium salts of diphenol mono and polysulfides.

Non-metallic detergents include compounds such as the phosphatides such as lecithin and oephlin, certain fatty oils as rapeseed oils, voltolized fatty or mineral oils and the like.

phenols as benzyl amino phenols; amines such as dibutyl-phenylene diamine, diphenyl amine, phenyl beta-naphthylamine, phenyl-alpha-naphthylamine and dibutylamine.

Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms, e. g. octadecenylsuccinic acid; alkali metal and alkaline earth metal salts of sulfonic acids and fatty acids, organic compounds containing an acidic radical in close proximity to a mercapto, nitrile, nitro or nitroso group (e. g. alpha cyano stearic acid).

Additional ingredients may comprise oil-soluble urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oil-soluble compounds.

Depending upon the additional additive used and conditions under which it is to be used, the amount of additive used may vary from 0.01 to 2% or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with reaction products of this invention.

This'invention is'a continuation-in-part of our copending application Serial No. 26,228, filed May 10, 1948 which has matured into U. S. Patent 2,573,568, and Serial No. 77,691, filed February 21, 1949, now patented June 10, 1952, Patent No. 2,599,761.

We claim as our invention:

1. A composition of matter comprising a major amount of a neutral liquid vehicle and a minor amount sufficient to impart extreme pressure properties to said vehicle of a mixture of phosphorus compounds having the general formula (1) wherein X is an element from the group consisting of O, S, Se and Te; R and R1 are organic radicals selected from the group consisting of alkyl, aryl, alkaryl and aralkyl, and R2 is a halogenated organic radical containing from 1 to 6 carbon atoms selected from the group consisting of polyhalogenated alkyl, polyhalogenated aryl, polyhalogenated alkaryl, and polyhalogenated aralkyl radicals, said halogen being not more than 4 carbon atoms removed from the phosphorus atom and (2) an organic phosphorus compound having the formulas:

wherein X is the same as defined above, wherein R3 and R4 are the same as R2 defined above but wherein the halogen is selected from the group consisting of chlorine and bromine and wherein said mixture of the compounds represented by (1) and (2) are present in the ratio of 1:2 to :1.

2. The composition of claim 1 but wherein R3 and R4 are alkyl radicals containing a total of 1 to 6- carbon atoms.

3. The composition of claim 1 wherein R3 and R4 are polyhalogenated alkyl radicals containing a total of from 1 to 6 carbon atoms.

4. The composition of claim 1 wherein the neutral vehicle is a liquid hydrocarbon.

5. The composition of claim 1 wherein the neutral vehicle is a synthetic polar containing lubricant.

6. The composition of claim 1 wherein the neutral vehicle is a mineral oil.

7. The composition of claim 1 wherein the neutral vehicle is di(2-ethylhexyl)sebacate.

8. A composition of matter comprising a major amount of mineral oil and a minor amount, sufficient to impart extreme pressure properties to said oil of a mixture of dibutyl trichloromethanephosphonate and trichloromethanephosphonic acid in the ratio of 1:2 to 2:1, respectively.

9. A composition of matter comprising a major amount of mineral oil and a minor amount, sufficient to impart extreme pressure properties to said oil of a mixture of diethyl trichloromethanephosphonate and trichloromethanephosphonic acid in the ratio of 1:2 to 2:1, respectively.

10. A composition of matter comprising a major amount of di(2-ethylhexyl')sebacate and a minor amount, sufiicient to impart extreme pressure properties to said ester of a mixture of dibutyl trichloromethanephosphonate and trichloromethanephosphonic acid in the ratio of 1:2 to 2:1, respectively.

11. A composition of matter comprising a major amount of di(2-ethylhexyl)sebacate and a minor amount, sufficient to impart extreme pressure properties to said ester of a mixture of diethyl trichloromethanephosphonate and trichloromethanephosphonic acid in the ratio of 1:2 to 2:1, respectively.

12. A composition of matter comprising a major amount of a mineral oil and a minor amount, sufiicient to impart extreme pressure properties to an oil of a mixture of a polyhaloalkane phosphonate and an organic phospho acid selected from the group consisting of an alkane phosphonic acid, an alkane phosphinic acid, a haloalkane phosphonic and a haloalkane phosphinic acid wherein the halogen atom has an atomic number of at least 17 and the halogens are not more than 4 carbon atoms removed from the phosphorus atoms, the total alkane radicals in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being present in the ratio of 1 :2 to 10 1, respectively.

13. A composition of matter comprising a major amount of a di-Z-ethylhexyl sebacate and a minor amount, sufficient to impart extreme pressure properties to an oil of a mixture of a polyhaloalkane phosphonate and an organic phospho acid selected from the group consisting of an alkane phosphonic acid, an alkane phosphinic acid, a haloalkane phosphonic and a haloalkane phosphinic acid wherein the halogen atom has an atomic number of at least 17 and the halogens are not more than 4 carbon atoms removed from the phosphorus atoms, alkane radicals in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being present inthe ratio of 1:2 to 10:1, respectively.

14. A composition of matter comprising a major amount of a mineral oil and a minor amount, sufficient to impart extreme pressure properties to an oil of a mixture of a polychloroalkane phosphonate and an organic phospho acid selected from the group consisting of an alkane phosphonic acid, an alkane phosphinic acid, a chloroalkane phosphonic and a chloroalkane phosphinic acid, said chloro atoms being not more than 4 carbon atoms removed from the phosphorus atoms, alkane radicals in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being present in the ratio of 1:2 to 10:1, respectively.

15. A composition of matter comprising a major amount of a di-2-ethylhexyl sebacate and a minor amount, suflicient to impart extreme pressure properties to an oil of a mixture of a polyohloroalkane phosphonate and an organic phospho acid selected from the group consisting of an alkane phosphonic acid, an alkane phosphinic acid, a chloroalkane phosphonic and a chloroalkane phosphinic acid, said chloro atoms being not more than 4 carbon atoms removed from the phosphorus atoms, alkane radicals in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being present in the ratio of 1 :2 to 10:1, respectively.

16. A composition of matter comprising a major amount of a mineral oil and a minor amount, sufficient to impart extreme pressure properties to said oil of a mixture 01 a polychloroalkane phosphonate and a polychloroalkane phosphonic acid, said chloro atoms being not more than 4 carbon atoms removed from the phosphorus atoms and the alkane radical in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being in the ratio of 1:2 to 10: 1, respectively.

17. A composition of matter comprising a major amount of a mineral oil and a minor amount, sufficient to impart extreme pressure properties to said 011 of a mixture of a polychloroalkane phosphonate and a polychloroalkane phosphinic acid, said chloro atoms being 13 not more than 4 carbon atoms removed from the phosphorus atoms and the total alkane radicals in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being in the ratio of 1 :2 to 10: 1, respectively.

18. A composition of matter comprising a major amount of di-2-ethylhexyl sebacate and a minor amount, sufiicient to impart extreme pressure properties to said oil of a mixture of a polychloroalkane phosphonate and a polychloroalkane phosphonic acid, said chloro atoms being not more than 4 carbon atoms removed from the phosphorus atoms and the alkane radical in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being in the ratio of 1:2 to 10: 1, respectively.

19. A composition of matter comprising a major amount of a di-Z-ethylhexyl sebacate and a minor amount, sufiicient to impart extreme pressure properties to said oil of a mixture of a polychloroalkane phosphonate and a polychloroalkane phosphinic acid, said chloro atoms being not more than 4 carbon atoms removed from the phosphorus atoms and the total alkane radicals in each of said phosphorus compounds having a total of from 1 to 6 carbon atoms, said mixture of said phospho compounds being in the ratio of 1:2 to 10:1, respectively.

DENHAM HARMAN.

ROY E. THORPE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,169,185 Shoemaker Aug. 8, 1939 2,174,019 Sullivan Sept. 26, 1939 2,311,306 Ritchey Feb. 16, 1943 2,495,799 Woodstock Jan. 31, 1950 OTHER REFERENCES Journal of the Institute of Petroleum, vol. 34, October 1948, pp. 758 and 759. 

1. A COMPOSITION OF MATTER COMPRISING A MAJOR AMOUNT OF A NEUTRAL LIQUID VEHICLE AND A MINOR AMOUNT SUFFICIENT TO IMPART EXTREME PRESSURE PROPERTIES TO SAID VEHICLE OF A MIXTURE OF PHOSPHORUS COMPOUNDS HAVING THE GENERAL FORMULA (1) 